LABORATORY EXPERIMENT

pubs.acs.org/jchemeduc

The Equilibrium Constant for Bromothymol Blue: A General Chemistry

Laboratory Experiment Using Spectroscopy
Elsbeth Klotz, Robert Doyle, Erin Gross,* and Bruce Mattson*
Department of Chemistry, Creighton University, Omaha, Nebraska 68178, United States
bS Supporting Information
ABSTRACT: A simple, inexpensive, and environmentally friendly under-
graduate laboratory experiment is described in which students use visible
spectroscopy to determine a numerical value for an equilibrium constant,
Kc. The experiment correlates well with the lecture topic of equilibrium
even though the subject of the study is an acid-base indicator, bromothy-
mol blue. The experiment gives excellent results and oers an inexpensive,
zero-waste alternative to traditional equilibrium experiments, such as the
Fe(SCN)2 equilibrium.
KEYWORDS: First-Year Undergraduate/General, Laboratory Instruction,
Hands-On Learning / Manipulatives, Acids/Bases, Equilibrium, Green
Chemistry, Physical Chemistry, Dyes/Pigments, UV-Vis Spectroscopy

e describe an update to a traditional determination of a

W pKa experiment, typically taught in general chemistry
during the acid-base unit. The experiment is presented so that
it could be integrated into a general equilibrium unit, prior to
acid-base chemistry. It is a simple, inexpensive, and environ-
mentally friendly undergraduate laboratory experiment in which
students use visible spectroscopy to determine a numerical value
for the equilibrium constant, Kc. It correlates well with the lecture
topic of equilibrium even though the subject of the study is an
acid-base indicator, bromothymol blue. The experiment gives
excellent results and oers a less expensivea and green alternative
to traditional equilibrium experiments, such as the Fe(SCN)2
equilibrium1-5 and I2/I3- equilibrium.6-8 The Fe(SCN)2
experiment uses 0.5 M nitric acid and generates heavy metal
waste. The I2/I3- experiment uses organic solvents or haloge-
nated organic solvents. This equilibrium experiment with bro-
mothymol blue produces aqueous waste at a neutral pH or a pH
that can easily be neutralized and uses small quantities of acids
and bases.
One of the oldest and most familiar quantitative equilibrium
experiments used in rst-year chemistry laboratory programs
involves the formation of the Fe(SCN)2 complex. Students use
spectrophotometry to calculate the formation constant of the
complex. Typically, students prepare a Beer-Lambert law plot
to determine the molar absorptivity of the complex. Then, under
conditions of dynamic equilibrium, they use the molar absorp-
tivity value to determine the equilibrium concentration of the
complex. Using an ICE table,9 students determine the
equilibrium concentration of all relevant species and calculate
Kc. Values for Kc vary dramatically with the concentration of
reagents, probably because other complexes such as Fe(SCN)2
form at higher thiocyanate concentrations.
Other experiments have been designed to determine the pKa of an
acid-base indicator in general chemistry using spectroph-
otometry.10,11 These experiments typically accompany the acid-base
unit during a general chemistry course. They generate little waste as
most solutions can be poured down the drain immediately after use or
after neutralization. They give accurate results when compared to
literature values. Because Ka is described by the general equilibrium
constant, Kc, this type of experiment can be modied to accompany
the chemical equilibrium unit.
EXPERIMENT
The experiment described here assumes that students have no
background in acid-base equilibria.b The primary focus of this
experiment is the determination of an equilibrium constant Kc for
a chemical equilibrium:
HBB H2 O H BB- H3 O 1
Published: March 04, 2011

Copyright r 2011 American Chemical Society and

Division of Chemical Education, Inc. 637 dx.doi.org/10.1021/ed1007102 | J. Chem. Educ. 2011, 88, 637639
Journal of Chemical Education LABORATORY EXPERIMENT

H3 O BB-  Scheme 1. Equilibrium of Bromothymol Bluea

Kc 2
HBB
where HBB is the acid form of bromothymol blue and BB- is the
basic form (Scheme 1). Students are given background informa-
tion on the Beer-Lambert law and spectrophotometry and the
chemical equation for the acid-base equilibrium of the indicator,
bromothymol blue. More detail on the student experimental
background and procedure can be found in the Supporting
Information.
The students derive an expression to calculate the equilibrium
a
The acidic form is HBB (yellow) and the basic form is BB- (blue). A
constant of the reaction using the absorbance data: mixture containing signicant quantities of each species would
appear green.
H3 O A616nm  A453nm
green yellow
Kc green 3
A453nm  Ablue
616nm

The absorbance measurements at 616 and 453 nm are the max

values for the base and acid forms of bromothymol blue,
respectively. Students make the four absorbance measurements
indicated in the equation along with a pH measurement and
calculate the value of Kc. If time permits or with appropriate
instrumentation, students can collect entire spectra of the yellow
and blue solutions and determine the max values. Sample spectra
are shown in Figure 1. If there is not time for students to collect
the spectra, they could be provided for students to view.
In a previous experiment using indicator (HIn) solutions,11
HIn H2 O H In- H3 O 4
students measured the absorbance at only the max of the basic
form, In-. Students use algebraic or graphical methods to
calculate pKa of the indicator using the expression: Figure 1. Visible absorbance spectra of bromothymol blue at low pH
(yellow, solid line) and high pH (blue, dashed line).
pKa pH logA - AIn- =AHIn - A 5
where A is the absorbance of the solution containing a certain Table 1. Student Absorbance Measurements
total concentration of the acid-base mixture, AIn- is the
Absorbance
absorbance of the base form at the same concentration, and
AHIn is the absorbance of the acid form at the same concentra- Wavelength/nm Yellow Solution Green Solution Blue Solution
tion. In the bromothymol blue experiment, students make
absorbance measurements at 616 and 453 nm on each solution 453 0.163 0.099 0.030
(yellow, green, and blue). In Figure 1, it can be seen that the blue 616 0.008 0.170 0.411
form absorbs near the max of the yellow form. Therefore, for the
green solutions, where both yellow and blue forms are present, pairs submitting results. Results were ultimately reported as pKc
the absorbance of the interfering form is subtracted. values for simpler comparison to the literature value of 7.1,
reported at an ionic strength of 0.1.12-15 Using eq 6, the
H3 O A616nm - A616nm  A453nm
green yellow yellow
Kc green 6 22 pairs of students obtained an average value for pKc of 7.04
A453nm - Ablue
453nm  A616nm
blue
( 0.03. A typical set of data obtained from one pair of students,
who also reported their green solution had a pH = 7.00, is given
More details on this procedure can be found in the Supporting in Table 1.
Information.
LEARNING OUTCOMES
HAZARDS
The student learning outcomes of this experiment are
Appropriate eye protection and clothing must be worn at all
To reinforce the concept that an equilibrium constant can
times. Use appropriate caution when handing 1 M HCl(aq) and
be calculated from concentration measurements (as learned
NaOH(aq) solutions. Both solutions are irritants at the concen-
in lecture).
trations used. All solutions should be neutralized before disposal. To use the Beer-Lambert law expressions to relate con-
Bromothymol blue may cause irritation to skin, eyes, and
centration to absorbance.
respiratory tract and may be harmful if swallowed or inhaled.
To reinforce laboratory techniques of using volumetric
glassware and spectrophotometry.
RESULTS To recognize good laboratory techniques with a compa-
In a laboratory test of this experiment, 22 pairs of students rison of the student-determined Kc value to the liter-
performed the experiment and calculations successfully out of 23 ature value.
638 dx.doi.org/10.1021/ed1007102 |J. Chem. Educ. 2011, 88, 637639
Journal of Chemical Education LABORATORY EXPERIMENT

ASSOCIATED CONTENT Raton, FL, 2007-2008, which referencesIndicators; Bishop, E., Ed.;
Pergamon: Oxford, 1972.
bS Supporting Information
Written directions used by students (including appropriate
safety instructions and CAS registry numbers for all chemicals);
instructor notes, including a color version of Figure 1 from the
manuscript, a photograph of bromothymol blue solutions (1-7)
in conditions of high pH to low pH, and absorbance spectra of
solutions 1-7; complete information regarding potential hazards
to students and instructors. This material is available via the
Internet at http://pubs.acs.org.

AUTHOR INFORMATION
Corresponding Author
*E-mails: (E.G.) eringross@creighton.edu, (B.M.) brucemattson@
creighton.edu.

ACKNOWLEDGMENT
The authors wish to acknowledge the Creighton University
Department of Chemistry. E.K. acknowledges support from the
Clare Boothe Luce Scholarship Program.

ADDITIONAL NOTE
a
Chemical costs ran $0.14/pair of students using 2009 prices
from Fisher. Using the same price list, the iron(III) thiocyanate
experiment costs approximately the same whereas the I2/I3-
experiment runs over $2.00/pair.
b
The experiment can serve as an introduction to the concepts of
pH, acids and bases, indicators, and buers and when those topics
are introduced later in the semester, experiences recalled from
this experiment will help with the segue. Students are called upon
to convert pH into the hydronium ion concentration.

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639 dx.doi.org/10.1021/ed1007102 |J. Chem. Educ. 2011, 88, 637639